The shortest symmetrical O-H⋯O hydrogen bond has a low-barrier double-well potential

John A. Belot, Joanna Clark, John A. Cowan, Gerard Harbison, Alexander I. Kolesnikov, Young Sik Kye, Arthur J. Schultz, Carter Silvernail, Xingang Zhao

Research output: Contribution to journalArticle

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Abstract

The strong hydrogen bond, in which a hydrogen atom is centered between two electronegative atoms in a single minimum potential has been widely discussed but rarely definitively observed. The compound 4-cyano-2,2,6,6-tetramethyl-3,5- heptanedione has the shortest symmetrical O-H⋯O hydrogen bond yet reported, at 239.3 pm. Neutron crystallography reveals the hydrogen-bonded proton to be nearly centered between the two oxygens, with a highly elongated thermal ellipsoid. Inelastic neutron scattering measurements of the normal and isotope labeled molecule reveal a hydrogen-bond vibrational frequency at 46.0 meV (371 cm -1). This frequency is too low to be compatible with a single-minimum potential and indicates a low-barrier double minimum. The temperature dependence of the NMR properties confirms the existence of a thermally accessible vibrationally excited state for the bond. Because other short hydrogen bonds show similar NMR behavior, it is likely that no "strong" hydrogen bond of this sort has yet been discovered.

Original languageEnglish (US)
Pages (from-to)6922-6926
Number of pages5
JournalJournal of Physical Chemistry B
Volume108
Issue number22
DOIs
StatePublished - Jun 3 2004

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Hydrogen bonds
hydrogen bonds
Hydrogen
Nuclear magnetic resonance
Atoms
nuclear magnetic resonance
Inelastic neutron scattering
Crystallography
Vibrational spectra
ellipsoids
Excited states
Isotopes
crystallography
Protons
hydrogen atoms
Neutrons
inelastic scattering
neutron scattering
isotopes
Oxygen

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Belot, J. A., Clark, J., Cowan, J. A., Harbison, G., Kolesnikov, A. I., Kye, Y. S., ... Zhao, X. (2004). The shortest symmetrical O-H⋯O hydrogen bond has a low-barrier double-well potential. Journal of Physical Chemistry B, 108(22), 6922-6926. https://doi.org/10.1021/jp0496710

The shortest symmetrical O-H⋯O hydrogen bond has a low-barrier double-well potential. / Belot, John A.; Clark, Joanna; Cowan, John A.; Harbison, Gerard; Kolesnikov, Alexander I.; Kye, Young Sik; Schultz, Arthur J.; Silvernail, Carter; Zhao, Xingang.

In: Journal of Physical Chemistry B, Vol. 108, No. 22, 03.06.2004, p. 6922-6926.

Research output: Contribution to journalArticle

Belot, JA, Clark, J, Cowan, JA, Harbison, G, Kolesnikov, AI, Kye, YS, Schultz, AJ, Silvernail, C & Zhao, X 2004, 'The shortest symmetrical O-H⋯O hydrogen bond has a low-barrier double-well potential', Journal of Physical Chemistry B, vol. 108, no. 22, pp. 6922-6926. https://doi.org/10.1021/jp0496710
Belot, John A. ; Clark, Joanna ; Cowan, John A. ; Harbison, Gerard ; Kolesnikov, Alexander I. ; Kye, Young Sik ; Schultz, Arthur J. ; Silvernail, Carter ; Zhao, Xingang. / The shortest symmetrical O-H⋯O hydrogen bond has a low-barrier double-well potential. In: Journal of Physical Chemistry B. 2004 ; Vol. 108, No. 22. pp. 6922-6926.
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